Exploratory studies of PM10 receptor and source profiling by GC/MS and principal component analysis of temporally and spatially resolved ambient samples.

For a recent exploratory study of particulate matter (PM) compositions, origins, and impacts in the El Paso/Juarez (Paso del Norte) airshed, the authors relied on solvent extraction (SX)-gas chromatography/mass spectrometry (GC/MS) procedures to characterize 24-hr quartz fiber (QF) filter samples obtained from nine spatially distributed high-volume (Hi-Vol) PM10 samplers as well as on thermal desorption (TD)-GC/MS methods to characterize 45 time-resolved (2-hr) filter samples obtained with modified 1-m3/hr PM10 samplers. Principal component analysis and related chemometric techniques were used for data reduction and data fusion as well as for multiway data correlation. A high degree of correspondence (R2 = 0.821) was found between the rapid TD-GC/MS method (which can be carried out on 2-hr filter slices containing only microgram amounts of sample) and conventional SX-GC/MS procedures. The four main source patterns of organic PM components observed in GC/MS profiles of both temporally and spatially resolved receptor samples obtained in the El Paso/Juarez border airshed during the study period are interpreted to represent (1) vehicular emissions plus resuspended urban dust; (2) biomass combustion; (3) native vegetation detritus and resuspended agricultural dust; and (4) waste burning. Moreover, principal component analysis of combined, variance-weighted, temporally resolved TD-GC/MS data and spatially resolved SX-GC/MS data was used to determine approximate source locations for specific PM components identified in time-resolved receptor sample profiles. The same approach can be used to determine approximate circadian concentration profiles of specific PM components identified in spatially resolved receptor sample profiles.

Characterization of fine particulate matter produced by combustion of residual fuel oil.

Combustion experiments were carried out on four different residual fuel oils in a 732-kW boiler. PM emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 microns in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the PM2.5 fraction consists of carbonaceous cenospheres and vesicular particles that range up to 10 microns in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As K-edges and at the Pb L-edge. Deconvolution of the X-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM2.5 samples than in the PM2.5+ samples. Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agreed fairly well with that of NiSO4, while most of the V spectra closely resembled that of vanadyl sulfate (VO.SO4.xH2O). The other metals investigated (i.e., Fe, Cu, Zn, and Pb) also were present predominantly as sulfates. Arsenic was present as an arsenate (As+5). X-ray diffraction patterns of the PM2.5 fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the loss on ignition (LOI) ranging from 64 to 87% for the PM2.5 fraction and from 88 to 97% for the PM2.5+ fraction. Based on 13C nuclear magnetic resonance (NMR) analysis, the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.

Extended theoretical considerations for Mass resolution in the resonance ejection mode of quadrupole Ion Trap Mass Spectrometry.

Proceeding from the pseudopotential-well approximation for ion motion in a quadrupole ion trap, mathematical expressions are derived to describe the excitation amplitude of an ion packet at a given mass-to-charge ratio. Ion-neutral collisions are incorporated to describe the damping of ion trajectories and to describe the distribution of individual ion trajectories about a mean amplitude for the ion packet. The rate of increase of the amplitude during scanning is related to expressions that describe the amplitude dispersion of the ions at the time of ejection from the trap, which is operating in a resonance ejection scanning mode to describe the temporal line width of the ejected ion packet. The temporal line width is related to mass resolution under a number of different scanning conditions. Included in the discussion are considerations of the effect on resolution of the resonance excitation voltage, temperature, pressure, noise, and buffer-gas composition. An expression for the maximum possible resolution at high ion mass-to-charge ratios is developed, and these results are compared to an existing theoretical construction. The expressions derived under the pseudopotential-well approximation are further extended to high q z values and compared to experimental data previously published by two other researchers.

Characterization of underivatized lipid biomarkers from microorganisms with pyrolysis short-column gas chromatography/ion trap mass spectrometry.

A microvolume Curie-point pyrolysis short-column (5 m) gas chromatography/mass spectrometry (Py-GC/MS) procedure was developed for the characterization of various lipid moieties in microorganisms. High linear flow rates (approximately 175 cm/s) characterized the GC conditions in order to effect an efficient chromatographic transfer and elution of the underivatized diglycerides and monoglycerides, and small modifications were necessary to the ion trap MS system in order for it to accommodate the relatively high gas load. During a typical analysis run anhydrodiacylglycerides eluted within a 5-6-min time frame. Gram-positive bacilli and Gram-negative species were differentiated from each other by the pyrolysis patterns of their lipid components. In spite of the complexity of the analyte, a straightforward visual analysis was achieved with the aid of simple computerized data display procedures. These procedures included examination of (1) total ion current (TIC) profiles of the lipid region of the reconstructed chromatogram, (2) the integrated mass spectrum of this region, (3) selected reconstructed ion chromatograms (RICs), (4) RIC intensity distributions, and (5) corresponding mass spectra. An appealing aspect of the lipid data reduction procedure is that most of it can be accomplished visually without requiring computerized pattern recognition techniques.

Pyrolytic methylation-gas chromatography of whole bacterial cells for rapid profiling of cellular Fatty acids.

A novel, on-line derivatization technique has been developed which enables generation of fatty acid methyl ester (FAME) profiles from microorganisms by gas chromatography-mass spectrometry without the need for laborious and time-consuming sample preparation. Microgram amounts of bacterial cells are directly applied to a thin ferromagnetic filament and covered with a single drop of methanolic solution of tetramethylammonium hydroxide. After air drying, the filament is inserted into a special gas chromatograph inlet equipped with a high-frequency coil, thus enabling rapid inductive heating of the ferromagnetic filament. This so-called Curie-point heating technique is shown to produce patterns of bacterial FAMEs which are qualitatively and quantitatively nearly identical to those obtained from extracts of methylated lipids prepared by conventional sample pretreatment methods. Relatively minor differences involve the loss of hydroxy-substituted fatty acids by the pyrolytic approach as well as strongly enhanced signals of FAMEs derived from mycolic acids. This type of pyrolysis enables on-line derivatization and thermal extraction of volatile derivatives for analysis, whereas the residual components remain on a disposable probe (ferromagnetic wire) of a pyrolytic device. The reduced sample size (micrograms instead of milligrams) and the lack of sample preparation requirements open up the possibility of rapid microbiological identification of single colonies (thus overcoming the need for time-consuming subculturing) as well as analysis of FAME profiles directly from complex environmental samples.

Spectrometric and chromatographic methods for the analysis of polymeric explant materials.

Several analytical pyrolysis methods, namely pyrolysis mass spectrometry (Py-MS), time-resolved pyrolysis mass spectrometry (TRPy-MS), and pyrolysis short column gas chromatography mass spectrometry (Py-GC/MS) were used to analyze polymers of clinical interest both before and after implantation. A sample of Biomer, a poly(ether urethane urea) used in the Utah artificial heart, was analyzed using these methods. Two poly(ether urethanes) (Tecoflex and Pellethane) and a poly(dimethylsilicone) (Silastic) sample were analyzed using Py-GC/MS. The direct Py-MS of Biomer identified the components used in the manufacture of Biomer. Py-GC/MS of Biomer, Tecoflex, Pellethane, and Silastic also identified the components used in their manufacture. The analysis of explanted Biomer detected the presence of adsorbed cholestadiene, the reaction of chloride ions with a stabilizer, and the presence of a siloxane contaminant. The cholestadiene was detected on the outside housing of an artificial heart which had been implanted for 297 days. The cholestadiene was detected at low levels and was identified by library search on the MS data system. The siloxane contaminant was also identified by the MS data system. All of the methods demonstrated required only short instrumental analysis times (10 min or less). Data analysis required much more time, but much of the data analysis can be automated.

Production of vinylidene chloride from the thermal decomposition of methyl chloroform.

This study investigated the extent to which methyl chloroform undergoes thermal decomposition to form vinylidene chloride. The experiment was conducted under laboratory conditions that approximate those found in industrial environments. Methyl chloroform vapors at approximately the TLV concentration of 1910 mg/m3 were passed through a heated quartz tube packed with glass or copper beads. In the presence of glass, the decomposition reaction began at 350 degrees C and was essentially complete at 605 degrees C. Vinylidene chloride was detected in nearly stoichiometric amounts. In the presence of copper, the reaction occurred initially at 180 degrees C. At 442 degrees C no methyl chloroform was detected. Once again, the conversion to vinylidene chloride was nearly complete. Two major conclusions have been derived from this study. First, under these experimental conditions, methyl chloroform undergoes thermal decomposition to yield substantial quantities of vinylidene chloride. Second, the dehydrohalogenation reaction proceeds at much lower temperatures in the presence of copper.

Pyrolysis mass spectrometry of bacteria from infected human urine. I. Influence of culturing and antibiotics.

Curie-point pyrolysis mass spectrometry was performed on three bacterial isolates obtained from infected human urine using a novel, direct isolation method. Bacterial samples were analysed directly after isolation, as well as after free growth in broth and after exposure to solutions containing penicillin and gentamicin. The spectra of bacteria directly from urine showed no detectable contamination from urinary constituents. Discriminant analysis indicated genetic strain differences to be greater than the combined variances due to sample preparation or the growth phase. Characteristic biochemical changes related to growth or non-growth were detectable after only 2 h of incubation. The potential usefulness of pyrolysis mass spectrometry techniques for rapid susceptibility testing is discussed.

Retrieval and analysis of a clinical total artificial heart.

Examination by light microscopy, scanning electron microscopy (SEM), and x-ray microanalysis of a clinical total artificial heart (TAH) implanted for 112 days revealed no evidence of calcification, pannus, or vegetative thrombus. A macroscopic thrombus was seen along the suture line in the right atrium but did not obstruct blood flow or valve function. Microscopic thrombi (less than 0.1 mm) and evidence of microemboli were observed on the pumping diaphragm using SEM. Characterization of selected polyetherurethane (PEU) samples from the pumping bladders and housing by Curie-point pyrolysis mass spectrometry (Py-MS) revealed unexpected differences between postmortem retrieved ventricles. Although the origin of these differences could be traced back to batch-to-batch variations in the original PEU material (Biomer), the precise nature of the observed differences in chemical structure and/or composition is still unknown. Numerical comparison between pyrolysis mass spectra from PEU samples exposed to blood or tissue and unexposed samples from the same ventricles did not detect evidence of biodegradation. Continual improvements in fabrication and quality control should minimize surface imperfections and ensure polymer reproducibility; however, existing materials and design parameters appear to be adequate for continued clinical implantation.

Pyrolysis mass spectrometry of complex organic materials.

Pyrolysis mass spectrometry in combination with computerized multivariate statistical analysis enables qualitative and quantitative analysis of nonvolatile organic materials containing molecular assemblies of a complexity and size far beyond the capabilities of direct mass spectrometry. The state of the art in pyrolysis mass spectrometry techniques is illustrated through specific applications, including structural determination and quality control of synthetic polymers, quantitative analysis of polymer mixtures, classification and structural characterization of fossil organic matter, and nonsupervised numerical extraction of component patterns from complex biological samples.

Pyrolysis mass spectrometry: a new method to differentiate between the mycobacteria of the 'tuberculosis complex' and other mycobacteria.

Pyrolysis mass spectrometry (p.m.s.) was applied to differentiate 91 coded mycobacteria as belonging to either the 'tuberculosis complex' (M. tuberculosis, M. bovis and M. bovis BCG) or to other species of Mycobacterium. Strains were analysed in batches; in each batch three strains each of M. tuberculosis, M. bovis and M. bovis BCG were included as references. Mass spectra were evaluated by computerized multivariate analysis. A 92% positive correlation with classical identification tests was found (2.2% false negative, 5.5% false positive). Approaches for further improvement of this score are indicated. High speed and complete automation of sample analysis, as well as computerized data-processing, make p.m.s. a potential tool for routine application. Sample transfer from peripheral laboratories to a p.m.s. facility is easy, as samples can be sterilized before shipping.

Analysis of streptococcal cell wall fractions by Curie-point pyrolysis gas-liquid chromatography.

A streptococcal strain, classified as Z(3)III was differentiated from its mutant strain, Z(3), lacking the type III polysaccharide antigen, by Curie-point pyrolysis gas-liquid chromatography. Differences observed in pyrograms of whole cells or cell envelopes of both strains could be directly related to the pyrolysis pattern of the purified type III antigen. The same results were obtained when streptococcus F III and its mutant were analyzed. Whereas the pyrolysis patterns of the type III antigen extracted from Z(3)III and F III bacteria were identical, marked differences were found in pyrograms of the serologically identical type III antigen isolated from the culture medium. Type III antigen was also easily differentiated from the purified type I, II and IV antigens. From the above findings it was concluded that pyrolysis gas-liquid chromatography can be used as a tool for the quality control and identification of streptococcal cell wall components.